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EP1558675A1 - Melanges contenant des stabilisateurs phenoliques et un agent de reduction - Google Patents

Melanges contenant des stabilisateurs phenoliques et un agent de reduction

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Publication number
EP1558675A1
EP1558675A1 EP03772266A EP03772266A EP1558675A1 EP 1558675 A1 EP1558675 A1 EP 1558675A1 EP 03772266 A EP03772266 A EP 03772266A EP 03772266 A EP03772266 A EP 03772266A EP 1558675 A1 EP1558675 A1 EP 1558675A1
Authority
EP
European Patent Office
Prior art keywords
mixture
phenolic
stabilizer
reducing agent
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03772266A
Other languages
German (de)
English (en)
Other versions
EP1558675B1 (fr
Inventor
Hauke Malz
Thomas Flug
Sylvia Rybicki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1558675A1 publication Critical patent/EP1558675A1/fr
Application granted granted Critical
Publication of EP1558675B1 publication Critical patent/EP1558675B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds

Definitions

  • the invention relates to mixtures containing amorphous phenolic stabilizers and at least one reducing agent, preferably at least one organophosphorus compound of trivial phosphorus, particularly preferably phosphite and / or phosphonite, and to processes for the preparation of an ester and / or amide, in particular a stabilizer, for example through condensation, e.g. Esterification, transesterification, amidation and / or amidation, preferably at least one phenolic carboxylic acid and / or one phenolic carboxylic acid derivative, with at least one alcohol and / or amine. Furthermore, the invention relates to plastics or lubricating oils containing the mixtures according to the invention.
  • Plastics such as polyurethanes, polyolefins, polyacetals, styrene and styrene copolymers, polyamides and polycarbonates are stabilized with thermal stabilizers to minimize the decrease in mechanical properties and the discoloration of the products due to oxidative damage.
  • Common antioxidants that are used in the art are e.g. phenolic stabilizers, which are offered under various brand names. Such phenolic stabilizers have also been described in general in the literature. Examples of commercial phenolic stabilizers are in Plastics Additive Handbook, 5th edition, H. Doubt, ed, Hanser Publishers, Kunststoff, 2001 ([1]), pages 98 to 107 and pages 116 to page 121.
  • phenolic stabilizers Due to their structure, phenolic stabilizers can be converted into products with a chromophoric character through various chemical reactions.
  • chromophore means that the substances absorb light in the visible range and thus contribute to the natural color of the stabilizer. To prevent discoloration of the plastic, all additives that have chromophoric properties are avoided. Also phenolic stabilizers containing substances with a chromophore character are therefore not used.
  • Such chromophores in phenolic stabilizers can already be formed during the synthesis of the stabilizer. Especially if the stabilizer is no longer replaced by e.g. If distillation or recrystallization is purified or, due to its structure, it cannot be purified, these chromophores formed during the synthesis can become a clear restriction on the quality and thus the usability of the stabilizer.
  • the aim of the present invention was therefore to develop stabilizers which have a minimum intrinsic color on ', ie where the proportion of the chromophoric impurities is reduced to a minimum in the stabilizer.
  • Another object of the present invention was to provide processes for the preparation of the phenolic stabilizers according to the invention, in particular processes for the preparation of an ester and / or amide, for example by condensation, e.g. To develop esterification, transesterification, transamidation and / or amidation, preferably at least one phenolic carboxylic acid and / or a phenolic carboxylic acid derivative with at least one alcohol and / or amine, which lead to phenolic esters and / or phenolic amides, in particular the phenolic stabilizer mixtures according to the invention that have the lowest possible intrinsic color, ie in which the proportion of chromophoric impurities in the product, in particular stabilizer mixture is reduced to a minimum.
  • the synthesis method should enable a uniform product quality, defined by the color number.
  • This object could be achieved by carrying out the esterification, transesterification, transamidation and / or amidation in the presence of at least one reducing agent, preferably at least one organophosphorus compound of trivalent phosphorus, particularly preferably phosphite and / or phosphonite. Due to the addition of the reducing agent to the reaction mixture with which the phenolic stabilizer is produced, the intrinsic color of the reaction product could be significantly reduced compared to phenolic stabilizers which were produced in the absence of reducing agents.
  • the particularly preferred phosphorus compounds can themselves serve as stabilizers and accordingly remain in the product mixture according to the invention containing the phenolic stabilizers and the reducing agents.
  • the advantage of the lower inherent color of the mixtures according to the invention is particularly evident in the case of amorphous stabilizers which cannot be cleaned of the chromophores by customary cleaning steps, such as, for example, crystallization, since these stabilizers according to the invention do not crystallize.
  • the production process according to the invention is based on the reaction of a phenolic active ingredient group (IA), preferably a phenolic carboxylic acid and / or a phenolic carboxylic acid derivative, with an anchor group (IB), i.e. a compound which has at least one hydroxyl group and / or at least one amino group.
  • an anchor group i.e. a compound which has at least one hydroxyl group and / or at least one amino group.
  • the connection between the active ingredient group (IA) and anchor group (IB) takes place via an A id and / or an ester group.
  • the corresponding acid can be used directly, but also suitable acid derivatives such as e.g.
  • Acid halides especially acid chlorides, acid anhydrides and other esters and / or amides of the acid, especially those with a volatile alcohol or amine
  • the acid or acid derivatives are in the presence of the reducing agent under otherwise customary conditions, preferably at a pressure between 1000 mbar and 10 mbar, at usually elevated temperatures, preferably 70 ° C. to 300 ° C., preferably 110 ° C. to 200 ° C., with alcohols and / or amines of the anchor group (IB). implemented to the desired esters and / or amides.
  • the methyl ester of an active ingredient group e.g. the methyl ester of the preferred or particularly preferred phenolic carboxylic acids, especially methyl 3- (3,5-tert-butyl-4-hydroxyphenyl) propionate
  • an anchor group e.g. an alkyl alcohol with an OH group and 7-9 carbon atoms and / or a polyethylene glycol with a number average molecular weight of 200 g / mol.
  • the reaction can optionally be carried out in the presence of customary catalysts.
  • catalysts can be used to accelerate the reaction, for example sulfonic acids such as toluenesulfonic acid or basic catalysts.
  • catalysts such as lithium hydroxide, lithium methylate, lithium methylate, potassium hydroxide, potassium methylate, potassium ethylate, potassium tert. -butylate, sodium hydroxide, sodium methylate, sodium ethylate or / or sodium tert-butoxide, but preferably potassium methylate and / or 5-potassium tert-butoxide.
  • Basic catalysts are preferred. It has been shown that it is advantageous not to add the catalyst to the reaction mixture all at once, but to gradually meter it in since the reaction time can be shortened in this way. Surprisingly, it has been shown that when using the above
  • the procedure can be, for example, that the anchor group (IB), e.g. a polyetherol with a number average
  • the reaction temperature is preferably from 120 ° C to
  • the potassium catalyst can then be separated off from the stabilizer according to the invention by generally known methods for separating potassium catalysts from polyetherols. For example, this can be done by using ion exchangers or by using phosphoric acid or hydrochloric acid.
  • stoichiometric refers to the amount of potassium ethylate used and can therefore vary, metered into the reaction mixture and stirred for 30 minutes.
  • the stabilizer can be used without further complex cleaning processes due to its low intrinsic color be used. It may be desirable to remove the reducing agent again. This can be done, for example, by distillation if the reducing agent is chosen so that its molar mass is significantly lower than that of the phenolic stabilizer.
  • carboxylic acids and / or carboxylic acid derivatives such as e.g. Acid halides, for example acid chlorides, acid anhydrides, esters and / or amides, are used which have a phenolic group.
  • the following phenolic carboxylic acids or derivatives of this carboxylic acid such as e.g. Acid halide, preferably acid chloride, acid anhydride, amide and / or ester, uses:
  • X, Y independently of one another hydrogen, straight-chain, branched-chain and / or cyclic alkyl group with 1 to 12 carbon atoms, preferably -C (CH)
  • Z Linear or branched alkylene radical with 1 to 12 carbon atoms, preferably -CH -CH-.
  • X, Y independently of one another hydrogen, straight-chain, branched-chain and / or cyclic alkyl group with 1 to 12 carbon atoms, preferably -C (CH 3 ) 3 .
  • the following carboxylic acid or a corresponding derivative of this carboxylic acid already shown is particularly preferably used as the active ingredient group (IA):
  • the synthesis of the phenolic active ingredient groups (IA) is generally known and regulations, for example for the synthesis of
  • 3- (3,5-Ditert. -Butyl-4-hydroxyphenyl) propionic acid methyl ester can be found in US 3644482 page 4 line 28 ff.
  • Butyl-4-hydroxyphenyl) propionic acid methyl ester can be, for example, 2,6-di-tert. -butylphenol and 0.1 to 10 mol% based on 2,6-di-tert. butylphenol, of a basic catalyst such as lithium hydroxide, lithium methylate, lithium methylate, potassium hydroxide, potassium methylate, potassium ethylate, potassium tert.
  • This metering is preferably carried out under a pressure which is greater than the vapor pressure of the methyl acrylate at the given reaction temperature. This ensures that the methyl acrylate is not removed from the reaction solution by evaporation. If working without pressure, the evaporated methyl acrylate is preferably returned to the reaction solution in reflux. 90 to 120 mol% of methyl acrylate, based on 2,6-di-tert-butylphenol, to the 2,6-di-tert are preferred. Butylphenol metered, but especially 95 to 110 mol%. After a reaction time of 60 to 180 minutes, the reaction is usually ended. The reaction product can then by neutralization of the alkaline catalyst and subsequent recrystallization or Rectification can be cleaned in a generally known manner.
  • methyl acrylate can preferably be removed from the reaction product, preferably for example at 50 to 80 ° C., in particular 60 ° C., preferably under vacuum and / or using a nitrogen propellant , and then the anchor group (IB) to the mixture containing the phenolic active ingredient group (IA) are added. After inerting and metering in the reducing agent, the transesterification reaction can then be continued as already described.
  • the advantage of this procedure which can be carried out in a reactor, lies in the efficient use of the reactor and the saving in the cleaning step.
  • the stabilizer is made from a sterically hindered phenol by chemical reaction, e.g. If transesterification or transamidation is carried out with an alcohol or amine, sterically hindered phenol can be prepared in situ. Alternatively, it can be prepared in a first reaction stage, isolated and then reacted with the alcohol or amine. In both cases, however, impurities may already arise during the production of the sterically hindered phenol, which leads to chromopores when the sterically hindered phenol is reacted further to the final stabilizer. The concentration of these chromophores can vary over a wide range. As a result, the individual stabilizer batches have different color numbers and, accordingly, no uniform quality can be delivered. By using the. Reducing agent can achieve a uniform product color even with different chromophore concentrations.
  • the anchor group (IB) is used, among other things, to adjust the molecular weight of the stabilizer, both via the molecular weight of the anchor group itself and via the number of hydroxyl and / or amino groups to which active ingredient groups (IA) can be bound.
  • the anchor group (IB) preferably has .1 to 20 hydroxyl groups and / or 0 to 20 amino groups.
  • the anchor group (IB) particularly preferably has 1 to 6, in particular 1 to 4, hydroxyl groups.
  • In the anchor group is environmentally compounds which are capable because of their hydroxyl and / or amino groups to advertising associated with the carboxyl function of the phenolic active group (IA) via an ester or amide group 'the.
  • the hydroxyl group (s) of the anchor group (IB) are preferably primary hydroxyl group (s), provided that hydroxyl groups and not exclusively amino groups are present.
  • ether can be used as anchor groups, for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycol and / or polytetrahydrofuran with a number average molecular weight of 120 to 3000 g / mol, for example a polyethylene glycol with a number average molecular weight of 200 g / mol or a Polytetrahydrofuran with an average number average molecular weight of 250 g / mol.
  • anchor groups for example diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycol and / or polytetrahydrofuran with a number average molecular weight of 120 to 3000 g / mol, for example a polyethylene glycol with a number average molecular weight of 200 g / mol or a Polytetrahydrofuran with an average number average molecular weight of 250 g / mol.
  • anchor groups known generally for the reaction with phenolic active groups for the production of phenolic stabilizers can also be used.
  • Monofunctional linear or branched alkyl alcohols having 7 to 18 carbon atoms are also preferably used, in particular a mixture consisting of monofunctional alkyl alcohols having 7 to 9 carbon atoms, the mixture having an average of 8 carbon atoms per alkyl alcohol.
  • a linear alkyl alcohol having 18 carbon atoms is also preferably used.
  • Monofunctional linear or branched alkyl alcohols with 13 to 15 carbon atoms are also preferably used.
  • reducing agents can be used as reducing agents, preferably phosphorus compounds and / or sodium dithionite, particularly preferably organophosphorus compounds of trivalent phosphorus, in particular phosphites and phosphonites.
  • suitable phosphorus compounds are, for example, triphenyl phosphite, diphenylalkylphosph.it, phenyldialkylphosph.it, tris (nonylphenyl) phosphite, trilaurylphosph.it, trioctadecylphosphite, di-stearyl-pentaerythritol diphosphite, tris (2, 4-di-tert- butylphenyl) phosphite, di-isodecylpentaerythritol diphosphite, di- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
  • phosphorus compounds can be found in Plastics Additive Handbook, 5th edition, H. Doubt, ed, Hanser Publishers, Kunststoff, 2001 ([1]), p.109-112.
  • Tris (nonylphenyl) phosphite, 4,4′-isopropylidenediphenol alkyl (C12-15) phosphite (CAS No: 96152-48-6), poly (dipropylene glycol) phenyl phosphite and / or tetraphenyl dipropylene glycol phosphite are preferably used.
  • the content of reducing agent in the reaction mixture for producing the phenolic stabilizer is preferably 0.01 to 10% by weight, based on the total mass of the mixture, particularly preferably 0.1 to 5% by weight, in particular 0.1 to 1 wt .-%.
  • the phenolic esters and / or amides produced by this process according to the invention are in the process product as
  • This mixture has the particular advantage that its color is particularly bright.
  • the reducing agent present in the mixture in particular the phosphites, do not have a disadvantageous effect when used to stabilize organic compounds, for example plastics or lubricating oils, since the phosphites also have a stabilizing effect.
  • the mixtures according to the invention which can thus be used directly as a stabilizer mixture, preferably have an iodine color number of ⁇ 5, particularly preferably 0 to 5, in particular 0 to 3, particularly preferably 0 to 1, measured in accordance with DIN 6162. Is the iodine number ⁇ 1 a definition of the color according to Hazen (DIN 53409) is recommended.
  • the particularly preferred stabilizers accordingly have a hazard number ⁇ 100, preferably from 0 to 100, particularly preferably a hazard number of ⁇ 70, in particular a hazard number from 0 to 70, particularly preferably of ⁇ 50. Such a low sparkleness cannot be achieved with conventional processes and can be attributed to the use of the reducing agent in the mixture.
  • the mixture according to the invention and the preferred embodiments of the mixtures result from the preferred starting materials already described at the beginning.
  • X, Y independently of one another hydrogen, straight-chain, branched-chain and / or cyclic alkyl group having 1 to 12, preferably 3 to 5 carbon atoms, particularly preferably -C (CH 3 ) 3
  • Z alkylene radical with 1 to 12 carbon atoms, preferably -CH 2 -CH-.
  • the phenolic stabilizer has at least one phenolic active ingredient group (IA) and at least one anchor group (IB), where (IA) and (IB) are connected via an ester and / or amide group and as (IB) at least a polyether, preferably polyethylene glycol and / or polytetrahydrofuran, with a molecular weight of 120 g / mol to 3000 g / mol is present.
  • a polyether preferably polyethylene glycol and / or polytetrahydrofuran
  • the n is chosen such that the number average Molecular weight of the stabilizer is between 700 g / mol and 800 g / mol.
  • N is particularly preferably selected such that in the collective, ie the stabilizer mixture comprising the individual stabilizer molecules, the weight-average molecular weight of the stabilizer mixture is greater than the number-average molecular weight of the stabilizer mixture.
  • ml, 2, 3, 4, 5, 6, 7, 8, 9 or 10 preferably 2, 3, 4, 5, or 6, particularly preferably 3 or 4.
  • the m is chosen such that the number-average Molecular weight of the stabilizer is between 700 g / mol and 900 g / mol. It is particularly preferred to choose such that in the collective, i.e. of the stabilizer mixture containing the individual stabilizer molecules, the weight average molecular weight of the stabilizer mixture is greater than the number average molecular weight of the stabilizer mixture.
  • Rl is an octadecyl radical or a linear or branched alkyl radical having 7 to 15, preferably 13 to 15 or 7 to 9 carbon atoms.
  • the weight ratio of phenolic stabilizer to reducing agent is preferably 10,000: 1 to 10: 1, particularly preferably 1000: 1 to 20: 1, in particular 1000: 1 to 100: 1.
  • the phenolic esters and / or amides according to the invention in a mixture with the reducing agents, in particular with the phosphates, are useful as stabilizers of organic materials which are usually subject to oxidative decomposition.
  • Such materials include: synthetic organic polymeric compounds, such as vinyl resins, which are formed in the polymerization of vinyl halides with unsaturated polymerizable compounds, for example vinyl esters, ⁇ , ⁇ -unsaturated aldehydes and unsaturated hydrocarbons, such as butadiene and styrene; Poly- ⁇ -olefins such as polyethylene, polypropylene, polyoxyethylene, polybutylene, polyisoprene and the like including the copolymers of poly- ⁇ -olefins; Polyurethanes, such as those made from polyols and organic polyisocyanates; Polyamides such as polyhexamethylene adipic acid amide and polycaprolactam; Polyesters, such as polymethylene terephthal
  • lubricating oils of the aliphatic ester type for example di- (2-ethylhexyl) azelate, pentaerythritol tetracaproate and the like
  • animal and vegetable oils for example linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil, corn oil, cottonseed oil and the like
  • Hydrocarbon materials such as gasoline, mineral oil, fuel oil, dry oils, cutting fluids, waxes, resins and rubber
  • Fatty acids such as soaps and the like.
  • the stabilizers according to the invention are preferred in all known thermoplastics, for example acrylic acid-butadiene-styrene copolymers (ABS), ASA, SAN, polyethylene, polypropylene, EPM, EPDM, PVC, acrylate rubber, polyester, polyoxymethylene (POM), Polyamide (PA), PC (polycarbonate) and / or thermoplastic polyurethanes, also referred to in this document as TPU, are used for stabilization, for example against UV radiation.
  • the stabilizers containing thermoplastic polyurethanes are preferably used.
  • thermoplastics in particular the TPU, preferably contain the phenolic stabilizers in an amount of 0.01 to 5% by weight, particularly preferably 0.1 to 2% by weight, in particular 0.3 to 1.5% by weight , each based on the weight of the thermoplastic.
  • phenolic stabilizers in addition to the stabilizers according to the invention, further generally known stabilizers can be used in the thermoplastics, for example further phosphites, but also thiosynergists, HALS compounds, UV absorbers, quenchers.
  • the stabilizers according to the invention and in particular mixtures containing the phenolic esters and / or amides can be added both to the compounds (b) reactive towards isocyanates before or during the production of the TPU and also to the finished TPU, for example the melted or softened TPU.
  • the thermal moplastische 'polyurethane can be melt processed without the effect of the stabilizers of the invention is lost. Methods of making TPU are well known.
  • thermoplastic polyurethanes can be reacted with (a) isocyanates with (b) isocyanate-reactive compounds with a molecular weight of 500 to 10,000 and optionally (c) chain extenders with a molecular weight of 50 to 499 optionally in the presence of (d) catalysts and / or (e) customary auxiliaries and / or additives are prepared, the reaction being carried out in the presence of the inhibitors according to the invention.
  • the starting components and methods for producing the preferred TPUs are shown below as examples.
  • the components (a), (b) and, if appropriate, (c), (e) and / or (f) normally used in the production of the TPU are to be described by way of example below:
  • organic isocyanates for example tri-,
  • TDI 2,4- and / or 2,6-tolylene diisocyanate
  • diphenylmethane diisocyanate 3,3 '-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate.
  • the generally known compounds which are reactive toward isocyanates can be used, for example polyesterols, polyetherols and / or polycarbonate diols, which are usually also grouped under the term "polyols", preferably with molecular weights of 500 to 8000 600 to 6000, especially 800 to 4000, and preferably a medium one
  • polyether polyols particularly preferably those polyetherols based on polyoxetetramethylene glycol.
  • the polyetherols have the advantage that they have a higher hydrolysis stability than polyesterols.
  • chain extenders for example diamines and / or alkanediols with 2 to 10 C.
  • Atoms in the alkylene radical in particular 1-butanediol, 1,6-hexanediol and / or di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols with 3 up to 8 carbon atoms, preferably corresponding oligo- and / or polypropylene glycols, it also being possible to use mixtures of the chain extenders.
  • Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the structural components (b) and (c) are the conventional tertiary amines known in the art, such as triethylamine, Dimethylcyclohexylamine, N-methylmorpholine, N, N '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds such as iron (III ) - acetylacetonate, tin compounds, for example tin diacetate, tin di-octoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like.
  • the catalysts are usually used in amounts of 0.0001 to 0.1 part by weight per 100 parts by weight of polyhydroxy compound (b).
  • customary auxiliaries (e) can also be added to the structural components (a) to (c). Examples include surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and
  • Pigments optionally in addition to the stabilizers according to the invention, further stabilizers, for example against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • the build-up components (b) and (c) can be varied in relatively wide molar ratios. Molar ratios of component (b) to chain extenders to be used overall have proven useful. (C) from 10: 1 to 1:10, in particular from 1: 1 ' to 1: 4, the hardness of the TPU also having. increasing content of (c) increases.
  • the conversion can be carried out using customary key figures, preferably a key figure of 60 to 120, particularly preferably a key figure of 80 to 110.
  • the key figure is defined by the ratio of the total isocyanate groups of component (a) used in the reaction to the groups reactive towards isocyanates, ie the active hydrogens, of components (b) and (c). If the index is 100, there is one active hydrogen atom for each isocyanate group of component (a), that is to say an isocyanate-reactive function of components (b) and (c). With key figures above 100, there are more isocyanate groups than OH groups.
  • the TPU can be produced continuously using the known processes, for example using reaction extruders or the belt process using one-shot or the prepolymer process, or batchwise using the known prepolymer process.
  • the components (a), (b) and optionally (c), (d) and / or (e) which are to be reacted can be mixed with one another in succession or simultaneously, the reaction commencing immediately.
  • the structural components (a), (b) and, if appropriate, (c), (d) and / or (e) are introduced into the extruder individually or as a mixture, for example at temperatures from 100 to 280 ° C., preferably 140 to 250 ° C brought to reaction, the TPU obtained is extruded, cooled and granulated.
  • the processing of the TPU according to the invention containing the stabilizers according to the invention is carried out to give the desired films, moldings, rollers, fibers, linings in automobiles, hoses, cable plugs, bellows, trailing cables, cable jackets, seals, belts or damping elements by conventional methods, such as injection molding or extrusion.
  • thermoplastic polyurethanes that can be produced by the process according to the invention, preferably the foils, molded parts, shoe soles, rollers, fibers, linings in automobiles, wiper blades, 5 hoses, cable plugs, bellows, trailing cables, cable sheathing, seals, belts or damping elements have the advantages described at the outset, ie a lower color through the use of a stabilizer with a particularly light color.
  • the potassium content was determined by means of atomic absorption spectroscopy and was below 20 ppm potassium for all experiments.
  • TIOP triisooctyl phosphite
  • TLP ' trilaurylphosph.it
  • TNPP tris (-4-n-nonylphenyl) phosphite
  • DHOP poly (dipropylene glycol) phenyl phosphite
  • TDP triisodecyl phosphite
  • THOP tetraphenyl diisopropylene glycol phosphite
  • Weston® 439 is a General Electric Speality product
  • the reflux condenser was then replaced by a distillation bridge and the excess MA was expelled for 30 minutes while nitrogen was continuously introduced. Thereafter, 268.1 g of a polyethylene glycol. with an OH number of 565 mg KOH / g, ie an average molecular weight of 198.58 g / mol, and the reducing agents given in Table 2 were added to the reaction mixture. The product was stirred at 140 ° C for 7 h. Nitrogen was still introduced. After this time, the finished phenolic stabilizer was cooled to 80 ° C. An amount equivalent to the catalyst (5.3 g) of 85% H P0 4 was added. After stirring for 30 minutes at 80 ° C., the precipitated salt was separated from the product at 90 ° C. using a heated pressure filter from SeitzSchenk (filter: type T750).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Polyethers (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP03772266A 2002-10-30 2003-10-28 Melanges contenant des stabilisateurs phenoliques et un agent de reduction Expired - Lifetime EP1558675B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10250768A DE10250768A1 (de) 2002-10-30 2002-10-30 Mischungen enthaltend phenolische Stabilisatoren
DE10250768 2002-10-30
PCT/EP2003/011932 WO2004039878A1 (fr) 2002-10-30 2003-10-28 Melanges contenant des stabilisateurs phenoliques et un agent de reduction

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EP1558675A1 true EP1558675A1 (fr) 2005-08-03
EP1558675B1 EP1558675B1 (fr) 2006-06-07

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EP (1) EP1558675B1 (fr)
JP (1) JP4869596B2 (fr)
KR (1) KR101021555B1 (fr)
CN (1) CN100460455C (fr)
AT (1) ATE328950T1 (fr)
AU (1) AU2003279325A1 (fr)
BR (1) BR0315266B1 (fr)
DE (2) DE10250768A1 (fr)
ES (1) ES2266874T3 (fr)
WO (1) WO2004039878A1 (fr)

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US7667066B2 (en) 2004-02-27 2010-02-23 Albemarle Corporation Preparation of sterically hindered hydroxyphenylcarboxylic acid esters
EP2300525A1 (fr) * 2008-07-11 2011-03-30 Basf Se Emulsions aqueuses et mélanges liquides de faible viscosité stables au stockage comme stabilisants
CA2861059C (fr) * 2012-01-27 2020-09-15 Dow Global Technologies Llc Procede pour reduire la couleur d'une huile lubrifiante usagee
TW201520253A (zh) * 2013-11-21 2015-06-01 Double Bond Chemical Ind Co 穩定劑以及包括該穩定劑的組成物
KR20180122523A (ko) 2017-05-02 2018-11-13 삼성디스플레이 주식회사 수지 조성물 및 이를 이용한 코팅층 제조 방법
EP3431521A1 (fr) 2017-07-20 2019-01-23 Basf Se Compositions d'agents de durcissement de couleur stable comprenant du polyisocyanate d'isocyanates (cyclo)aliphatiques
JP7532914B2 (ja) * 2019-07-19 2024-08-14 日本ゼオン株式会社 保存安定性に優れるアクリルゴムシート
CA3203263A1 (fr) 2020-12-23 2022-06-30 Scott Capitosti Composes de benzazepine utilises en tant qu'antioxydants pour compositions lubrifiantes
CN113121878B (zh) * 2021-04-20 2022-12-09 山东省临沂市三丰化工有限公司 一种复合液体受阻酚类抗氧剂及其制备方法

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US7625849B2 (en) 2009-12-01
US20060122076A1 (en) 2006-06-08
CN1711314A (zh) 2005-12-21
WO2004039878A1 (fr) 2004-05-13
JP2006504818A (ja) 2006-02-09
KR101021555B1 (ko) 2011-03-16
CN100460455C (zh) 2009-02-11
ES2266874T3 (es) 2007-03-01
BR0315266B1 (pt) 2013-07-30
BR0315266A (pt) 2005-08-23
EP1558675B1 (fr) 2006-06-07
DE50303738D1 (de) 2006-07-20
ATE328950T1 (de) 2006-06-15
JP4869596B2 (ja) 2012-02-08
DE10250768A1 (de) 2004-05-13
KR20050084619A (ko) 2005-08-26
AU2003279325A1 (en) 2004-05-25

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